Isolation, formulation and shaping of macrocyclic oligoesters

ABSTRACT

Processes for isolating, formulating, and shaping macrocyclic oligesters were developed which allow efficient production of macrocyclic oligoesters substantially free from solvent, which may include additives, fillers, and catalysts.

RELATED APPLICATIONS

[0001] This application claims the benefit of the filing date of U.S.Provisional Application Ser. No. 60/301,399, filed on Jun. 27, 2001,entitled “Melt Isolation, Solidification, and Formulation of MacrocyclicOligoesters,” which is incorporated by reference herein in its entirety.

TECHNICAL FIELD

[0002] The invention relates generally to thermoplastics and articlesformed therefrom. More particularly, the invention relates to processesfor isolating, formulating, and shaping macrocyclic oligoesters such asmacrocyclic oligoesters of 1,4-butylene terephthalate.

BACKGROUND INFORMATION

[0003] Linear polyesters such as poly(alkylene terephthalate) aregenerally known and commercially available where the alkylene typicallyhas 2 to 8 carbon atoms. Linear polyesters have many valuablecharacteristics including strength, toughness, high gloss, and solventresistance. Linear polyesters are conventionally prepared by thereaction of a diol with a dicarboxylic acid or its functionalderivative, typically a diacid halide or ester. Linear polyesters may befabricated into articles of manufacture by a number of known techniquesincluding extrusion, compression molding, and injection molding.

[0004] Recently, macrocyclic oligoesters were developed that have uniqueproperties that make them attractive for a variety of applications,including as matrices for engineering thermoplastic composites.Macrocyclic oligoesters exhibit low melt viscosity, for example,allowing them easily to impregnate a dense fibrous preform followed bypolymerization to polymers. Furthermore, certain macrocyclic oligoestersmelt and polymerize at temperatures well below the melting point of theresulting polymer. Upon melting and in the presence of an appropriatecatalyst, polymerization and crystallization can occur virtuallyisothermally.

[0005] Production of macrocyclic oligoesters such as macrocyclic(1,4-butylene terephthalate) typically involves the use of one or moresolvents such as o-dichlorobenzene or xylene. Some prior techniques thathave been used to recover macrocyclic oligoesters dissolved in a solventrequired the addition of a large amount of anti-solvent to the solutionto precipitate the macrocyclic oligoester followed by collection of theproduct using a filter or a centrifuge. The use of anti-solvents resultsin increased processing complexity, costs, and creates additionalenvironmental storage and disposal concerns.

[0006] Linear polyesters may be depolymerized to form macrocyclicoligoesters. The product solution of a depolymerization reaction may bedilute, making recovery more time consuming. Depolymerization productionefforts also generally take place in stages, with each stage including astep of the process and with intermediate storage between the steps.

SUMMARY OF THE INVENTION

[0007] There is a need for effective, efficient, and low cost processesfor isolating, formulating, and shaping macrocyclic oligoesters. Thereis also a need for processes that enable continuous production ofmacrocyclic oligoesters. In one aspect, the invention generally relatesto processes for producing macrocyclic oligoesters (e.g., macrocyclic1,4-butylene terephthalate oligomers), including processes for isolatingmacrocyclic oligoesters from solvents so the resulting macrocyclicoligoesters are substantially free from solvent. The invention alsoincludes processes for formulating and shaping the substantially solventfree macrocyclic oligoesters. In some embodiments, the describedprocesses are performed continuously, to enable continuous production ina manufacturing plant. Further, the described processes can bebeneficially combined for greater efficiencies and production benefits.

[0008] In one aspect, the invention features a process for isolating amacrocyclic oligoester. A solution including a macrocyclic oligoesterand a solvent is provided. The macrocyclic oligoester typically has astructural repeat unit of formula (I):

[0009] where R may be an alkylene, a cycloalkylene, or a mono- orpolyoxyalkylene group, and A may be a divalent aromatic or alicyclicgroup. The solvent is then removed without the use of anti-solvent. Intypical practice, substantially all of the solvent is removed. In oneembodiment, the solvent is removed under elevated temperatureconditions. In another embodiment, the solvent is removed under reducedpressure conditions. In another embodiment, the solvent is removed undera combination of both elevated temperature and reduced pressureconditions. The macrocyclic oligoester, which is substantially free fromthe solvent then typically is collected. In one embodiment, the solventis continuously removed from the solution. In another embodiment, themacrocyclic oligoester substantially free from the solvent iscontinuously collected.

[0010] In another aspect, the invention features a process for shaping apartially-crystallized macrocyclic oligoester. In one embodiment, thisprocess includes providing a substantially solvent-free moltenmacrocyclic oligoester typically having the structural repeat unit ofthe formula (I) described above. The substantially solvent-free moltenmacrocyclic oligoester is sheared to form a partially-crystallizedmacrocyclic oligoester. The partially-crystallized macrocyclicoligoester is then shaped. In one embodiment, a continuous flow ofsubstantially solvent-free molten macrocyclic oligoester is shearedcontinuously. In another embodiment, the step of shaping thepartially-crystallized macrocyclic oligoester is conducted continuously.

[0011] In yet another aspect, the invention features a process formaking a prepreg of a macrocyclic oligoester and a polymerizationcatalyst. In one embodiment, a mixture of a molten macrocyclicoligoester and a polymerization catalyst, which is substantially freefrom any solvent, is provided. The macrocyclic oligoester typically hasthe structural repeat unit of the formula (I) described above. Themixture is deposited onto a fabric material, forming a prepreg. In oneembodiment, the mixture is partially-crystallized prior to beingdeposited onto the fabric material.

[0012] In yet another aspect, the invention features a process formaking a prepreg of a macrocyclic oligoester and a polymerizationcatalyst. In one embodiment, a mixture of a molten macrocyclicoligoester and a polymerization catalyst, which is substantially freefrom any solvent, is provided continuously. The macrocyclic oligoestertypically has the structural repeat unit of formula (I) described above.The mixture of the macrocyclic oligoester and the polymerizationcatalyst is crystallized partially and deposited onto a fabric material.

[0013] In still another aspect, the invention features a process forformulating a macrocyclic oligoester. In one embodiment, a solutionincluding a macrocyclic oligoester and a solvent is provided. Themacrocyclic oligoester typically has a structural repeat unit of formula(I) described above. The solvent often is continuously removed from thesolution at a temperature between about 180° C. and about 200° C. and ata pressure between about atmospheric pressure and about 10 torr. Thestep of solvent removal produces a substantially solvent-free moltenmacrocyclic oligoester. The substantially solvent-free moltenmacrocyclic oligoester then is sheared at a temperature below themelting point of the molten macrocyclic oligoester. In one embodiment,the shearing temperature is maintained between about 145° C. and about155° C., thereby forming a partially-crystallized macrocyclicoligoester. The partially-crystallized macrocyclic oligoester is shapedinto one or more shapes such as a pellet, a pastille, and/or a flake.

BRIEF DESCRIPTION OF FIGURES

[0014]FIG. 1 is a schematic flow diagram of an embodiment of a solventremoval system.

[0015]FIG. 2 is a schematic flow diagram of an embodiment of a solventremoval system.

[0016]FIG. 3 is a schematic flow diagram of an embodiment of a solventremoval system.

[0017]FIG. 4 is a schematic flow diagram of an embodiment of a solventremoval system.

[0018]FIG. 5 is a schematic flow diagram of an embodiment of a processfor making pellets from a macrocyclic oligoester.

[0019]FIG. 6 is a schematic flow diagram of an embodiment of apastillation process (e.g., making prepregs from a macrocyclicoligoester).

[0020]FIG. 7 is a schematic illustration of an embodiment of a processfor making a prepreg from a macrocyclic oligoester.

[0021]FIG. 8 is a schematic flow diagram of an embodiment of a solventremoval system.

[0022]FIG. 9 is a schematic flow diagram of an embodiment of a systemfor shaping macrocyclic oligoesters from a solution of macrocyclicoligoester and solvent.

[0023]FIG. 10 is a schematic flow diagram of an embodiment of a systemfor shaping macrocyclic oligoesters from a solution of macrocyclicoligoester and solvent.

DESCRIPTION

[0024] The processes of the invention are more efficient and economicalthan existing techniques because the isolation, formulation, and shapingprocesses may be carried out continuously and on a large scale. Thepurity of the macrocyclic oligoester may be effectively controlled bythe incorporation of multiple solvent removal apparatus where necessary.The isolation, formulation, and shaping processes also may bebeneficially linked, resulting in efficient mass production and loweredmanufacturing costs. Such linked processes avoid product and energywaste incurred when the isolation, formulation, and shaping processesare conducted separately. For example, macrocyclic oligoesters may beisolated in a molten state. The shaping process typically requires themacrocyclic oligoesters to be provided in a molten state. Accordingly,linking these processes reduces energy uses and increases productionefficiency.

[0025] For example of the benefits of continuous production, amacrocyclic oligoester having between about 80 ppm and about 400 ppmsolvent may be produced at a rate of between about 40 kg/hr and about300 kg/hr using a feed solution having 20% by weight of macrocyclicoligoester, which can be fed at a rate of between about 200 kg/hr andabout 1,500 kg/hr. For example, after solvent removal, the macrocyclicoligoester, which is substantially free from solvent, may be collectedat a rate of between about 80 kg/hr to about 250 kg/hr. Pellets andpastilles of formulated and shaped macrocyclic oligoesters also can beproduced at a similar rate.

[0026] Definitions

[0027] The following general definitions may be helpful in understandingthe various terms and expressions used in this specification.

[0028] As used herein, a “macrocyclic” molecule means a cyclic moleculehaving at least one ring within its molecular structure that contains 8or more atoms covalently connected to form the ring.

[0029] As used herein, an “oligomer” means a molecule that contains 2 ormore identifiable structural repeat units of the same or differentformula.

[0030] As used herein, an “oligoester” means a molecule that contains 2or more identifiable ester functional repeat units of the same ordifferent formula

[0031] As used herein, a “macrocyclic oligoester” means a macrocyclicoligomer containing 2 or more identifiable ester functional repeat unitsof the same or different formula. A macrocyclic oligoester typicallyrefers to multiple molecules of one specific formula having varying ringsizes. However, a macrocyclic oligoester may also include multiplemolecules of different formulae having varying numbers of the same ordifferent structural repeat units. A macrocyclic oligoester may be aco-oligoester or a higher order oligoester, i.e., an oligoester havingtwo or more different structural repeat units having an esterfunctionality within one cyclic molecule.

[0032] As used herein, “an alkylene group” means —C_(n)H_(2n)—, wheren≧2.

[0033] As used herein, “a cycloalkylene group” means a cyclic alkylenegroup, —C_(n)H_(2n-x-), where x represents the number of H's replaced bycyclization(s).

[0034] As used herein, “a mono- or polyoxyalkylene group” means[—(CH₂)_(m)—O—]_(n)—(CH₂)_(m)—, wherein m is an integer greater than 1and n is an integer greater than 0.

[0035] As used herein, “a divalent aromatic group” means an aromaticgroup with links to other parts of the macrocyclic molecule. Forexample, a divalent aromatic group may include a meta- or para-linkedmonocyclic aromatic group (e.g., benzene).

[0036] As used herein, “an alicyclic group” means a non-aromatichydrocarbon group containing a cyclic structure therein.

[0037] As used herein, “partially-crystallized macrocyclic oligomer”means a macrocyclic oligomer at least a portion of which is incrystalline form. Partially-crystallized macrocyclic oligomer may havevarious degrees of crystallinity ranging from 1% crystalline to 99%crystalline. Crystallinity imparts handleablility to the macrocyclicoligomer, enabling it to be shaped, for example.

[0038] As used herein, “a continuous process” means a process thatoperates on the basis of a continuous flow of materials into and/ormaterials out of the process.

[0039] As used herein, “a polyester polymer composite” means a polyesterpolymer that is associated with another substrate such as a fibrous orparticulate material. Illustrative examples of particulate material arechopped fibers, glass microspheres, and crushed stone. Certain fillersand additives thus can be used to prepare polyester polymer composites.A fibrous material means more substrate, e.g., fiberglass, ceramicfibers, carbon fibers or organic polymers such as aramid fibers.

[0040] As used herein, “a fabric material” means any substrate useful inreceiving macrocyclic oligoesters during production and formulationprocesses and in preparing prepregs of macrocyclic oligomers. Typically,fabric materials include fiber tow, fiber web, fiber mat, and fiberfelt. The fabric materials may be woven or non-woven, unidirectional, orrandom.

[0041] Macrocyclic Oligoesters

[0042] Macrocyclic oligoesters that may be processed according toprocesses of this invention include, but are not limited to, macrocyclicpoly(alkylene dicarboxylate) oligomers typically having a structuralrepeat unit of the formula:

[0043] wherein R is an alkylene, a cycloalkylene, or a mono- orpolyoxyalkylene group; and A is a divalent aromatic or alicyclic group.

[0044] Preferred macrocyclic oligoesters are macrocyclic oligoester of1,4-butylene terephthalate, 1,3-propylene terephthalate,1,4-cyclohexylenedimethylene terephthalate, ethylene terephthalate,propylene terephthalate, and 1,2-ethylene 2,6-naphthalenedicarboxylate,and macrocyclic co-oligoesters comprising two or more of the abovestructural repeat units.

[0045] Synthesis of the macrocyclic oligoesters may be achieved bycontacting at least one diol of the formula HO—R—OH with at least onediacid chloride of the formula:

[0046] where R and A are as defined above. The reaction typically isconducted in the presence of at least one amine that has substantiallyno steric hindrance around the basic nitrogen atom. An illustrativeexample of such amines is 1,4-diazabicyclo[2.2.2]octane (DABCO). Thereaction usually is conducted under substantially anhydrous conditionsin a substantially water immiscible organic solvent such as methylenechloride. The temperature of the reaction typically is within the rangeof from about −25° C. to about 25° C. See, e.g., U.S. Pat. No. 5,039,783to Brunelle et al.

[0047] Macrocyclic oligoesters also can be prepared via the condensationof a diacid chloride with at least one bis(hydroxyalkyl)ester such asbis(4-hydroxybutyl) terephthalate in the presence of a highly unhinderedamine or a mixture thereof with at least one other tertiary amine suchas triethylamine. The condensation reaction is conducted in asubstantially inert organic solvent such as methylene chloride,chlorobenzene, or a mixture thereof See, e.g., U.S. Pat. No. 5,231,161to Brunelle et al.

[0048] Another method for preparing macrocyclic oligoesters ormacrocyclic co-oligoesters is the depolymerization of linear polyesterpolymers in the presence of an organotin or titanate compound. In thismethod, linear polyesters are converted to macrocyclic oligoesters byheating a mixture of linear polyesters, an organic solvent, and atransesterification catalyst such as a tin or titanium compound. Thesolvents used, such as o-xylene and o-dichlorobenzene, usually aresubstantially free from oxygen and water. See, e.g., U.S. Pat. No.5,407,984 to Brunelle et al. and U.S. Pat. No. 5,668,186 to Brunelle etal.

[0049] It is also within the scope of the invention to processmacrocyclic co- and higher order oligoesters using the methods of theinvention. Therefore, unless otherwise stated, an embodiment of acomposition, article, or process that refers to macrocyclic oligoestersalso includes embodiments utilizing macrocyclic co-oligoesters andhigher order oligoesters.

[0050] Isolation of Macrocyclic Oligoesters

[0051] In one aspect, the invention generally features processes forisolating a macrocyclic oligoester from a solution having a macrocyclicoligoester and a solvent in a manner that does not require use of ananti-solvent. In one embodiment, the process includes removing solventto yield a macrocyclic oligoester substantially free from solvent. Asolution including a macrocyclic oligoester and a solvent is provided.The solvent is then removed without the use of anti-solvent. In oneembodiment, the solvent is removed under reduced temperature conditions.In another embodiment, the solvent is removed under elevated pressureconditions. In another embodiment, the solvent is removed under acombination of both elevated temperature and reduced pressureconditions. The macrocyclic oligoester substantially free from thesolvent then typically is collected. In one embodiment, the solvent iscontinuously removed from the solution including a macrocyclicoligoester and a solvent. In another embodiment, the macrocyclicoligoester substantially free from the solvent is continuouslycollected.

[0052] There is no limitation to the concentration of macrocyclicoligoester in the solution. In one embodiment, the solution of amacrocyclic oligoester and a solvent (the input or feed solution)contains between about 1% and about 50% by weight macrocyclicoligoester. In other embodiments, the feed solution contains betweenabout 3% and about 50%, between about 5% and about 40%, between about 5%and about 20%, between about 3% and about 10%, or between about 1% toabout 3% by weight macrocyclic oligoester. The solution may contain oneor two or more different solvents. “Solvent” used herein refers to thesolvent or solvents contained in the feed solution.

[0053] Solvent removal may be carried out at an elevated temperature, ata reduced pressure, or both. In one embodiment, the feed solution isheated at an elevated temperature and a reduced pressure to remove thesolvent from the solution. The resulting macrocyclic oligoester issubstantially free from solvent. A macrocyclic oligoester issubstantially free from solvent if the solvent content is less than 200ppm. Preferably, the solvent content is less than 100 ppm. Morepreferably the solvent content is less than 50 ppm or less than 10 ppm.

[0054] The processing temperature and pressure for solvent removal areselected according to factors including the solvent to be removed, thesolvent removal device(s) used, the desired time of purification, andthe macrocyclic oligoester being isolated. In one embodiment, the stepof removing solvent is conducted at a temperature within a range fromambient temperature to about 300° C. In other embodiments, the step ofremoving solvent is conducted from about 200° C. to about 260° C., fromabout 230° C. to about 240° C., or from about 180° C. to about 200° C.

[0055] The pressure at which solvent removal is conducted can vary fromatmospheric pressure to about 0.001 torr. In one embodiment, thepressure is within a range from 0.001 torr to about 0.01 torr. In otherembodiments, the pressure is within a range from atmospheric pressure toabout 10 torr, from about 10 torr to about 5.0 torr, from about 5.0 torrto about 1.0 torr, from about 1.0 torr to about 0.1 torr, or from about0.1 torr to about 0.01 torr.

[0056] Solvent removal may be accomplished in almost any apparatus,e.g., vessels or devices or a combination of apparatus. Non-limitingexamples of solvent removal apparatus that may be employed include arising film evaporator, a falling film stripper, a thin film evaporator,a wiped film evaporator, a molecular still, a short path evaporator, acentrifuge, and a filter. The terms evaporator and stripper may be usedinterchangeably. In one embodiment, the rising film evaporator may be atubular heat exchanger. A rising film evaporator is an apparatus used tovaporize part or all of the solvent from a solution where the solutionis introduced to the bottom of the evaporator. A falling film stripperis an evaporative device for the removal of vapors from solution, wherethe solution is introduced to the top of the apparatus and travels tothe bottom of the apparatus. A thin film evaporator is an apparatus thatgenerates and exposes a thin film of material for evaporation and hasthe vapor condenser outside of the evaporator. A wiped film evaporatoris an apparatus that generates and exposes a thin film of material towiping or agitation to provide evaporation. A short path evaporatorgenerates and exposes a thin film of material for evaporation and hasthe vapor condenser inside the evaporator. In some embodiments, theshort path evaporator exposes the thin film to wiping or agitation toprovide evaporation. A molecular still is an apparatus that utilizes acondenser inside the body of the still. One or more solvent removaldevice may be employed in accordance with the invention. In oneembodiment, each solvent removal apparatus used in the process removesbetween about 80% and about 90% of the solvent. In one embodiment,multiple solvent removal apparatus are employed to achieve the desireddryness in the macrocyclic oligoester substantially free from solvent.

[0057]FIG. 1 schematically illustrates one embodiment of a solventremoval system 2. An input solution 10 is pumped into a rising filmevaporator 11. As the input solution travels up the first rising filmevaporator 11, some of the solvent vaporizes and is separated from thesolution. This solution and the vapor then travels through a flashdevice 15. A flash device is an apparatus that is used to separate theliquid and the gas phase. The liquid phase solution then is pumped intoa second rising film evaporator 21. After traveling through anotherflash device 25, the vapor phase solvent that is removed from flashdevices 15 and 25 is pumped through paths 20′ and 20″, respectively, andis condensed in condensers 52 and 54. The condensers 52 and 54 changeany vapor phase solvent in paths 20′ and 20″ into a liquid phase.Optionally, effluent containing removed solvent may be discharged fromcondensers 52 and 54. The condensed solvent is then collected in theliquid receiver 27. The solution containing macrocyclic oligoester ispumped from flash device 25 into a falling film stripper 31. In oneembodiment, the vapors removed in the falling film stripper 31 alsotravel through the flash device 25. An output product 130, which issubstantially free from solvent, is pumped out of the falling filmstripper 31. In one embodiment, the output product 130 is molten.

[0058] Substantially all of the solvent in the input solution can beremoved from the macrocyclic oligoester to form a macrocyclic oligoestersubstantially free from solvent In one embodiment, the macrocyclicoligoester substantially free from solvent may contain about 200 ppm orless of solvent. In other embodiments, the macrocyclic oligoestersubstantially free from solvent may contain about 100 ppm or less ofsolvent, about 50 ppm or less of solvent, and about 10 ppm or less ofsolvent The amount of solvent remaining in the macrocyclic oligoestersubstantially free from solvent may be measured using chromatographictechniques such as gas chromatography, GCMS, or HPLC.

[0059] In determining an appropriate solvent stripping system to employin a particular process, factors that need to be considered include theconcentration of macrocyclic oligoester in the feed solution, thedesired dryness and/or purity of the product, the solvent to be removed,and the desired length of time for solvent removal. For example,starting with a relatively dilute feed solution (i.e., low percentage ofmacrocyclic oligoester), more solvent removal steps and/or time may benecessary to produce a substantially solvent free macrocyclicoligoester. Conversely, a concentrated feed solution of macrocyclicoligoester may require fewer solvent removal steps and/or time.

[0060] Generally and in one embodiment, solvent is removed from an inputsolution by exposing the input solution to an elevated temperature and areduced pressure in a first rising film evaporator. The input solutionthen travels to a second rising film evaporator where it is exposed toan elevated temperature and a reduced pressure. Finally, the inputsolution travels to a falling film stripper and a macrocyclic oligoestersubstantially free from solvent is collected from the falling filmstripper.

[0061] In another general embodiment, solvent is removed from an inputsolution by exposing the feed solution to an elevated temperature and areduced pressure in a first rising film evaporator. The input solutionthen travels through a first flash device. The solvent that is removedin the first rising film evaporator and the first flash device travelsto a first condenser and the remainder of the input solution travels toa second rising film evaporator where it is exposed to an elevatedtemperature and a reduced pressure. The input solution then travelsthrough a second flash device. The solvent that is removed in the secondrising film evaporator and the second flash device travels to a secondcondenser. The solvent that has traveled through the first condenser andthe second condenser is transported to a liquid receiver. The remainderof the input solution and the solvent travels to a falling filmstripper. Optionally, the sparger may operate at the same time as thefalling film stripper. Alternatively, a sparger removes gasses andvapors from the input solution after it has traveled through thestripper. Thereafter, a macrocyclic oligoester substantially free fromsolvent is collected.

[0062] When preparing macrocyclic oligoesters by depolymerizing linearpolyesters, dilute conditions may be desired to promote cyclization andto increase the yield of macrocylcic oligoesters. As a result, themacrocyclic oligoester solution (e.g., the product solution of adepolymerization reaction) may be dilute (e.g., a 1% by weightmacrocyclic oligoester solution).

[0063]FIG. 2 schematically illustrates an embodiment of a system 1 forsolvent removal that is typically employed where the solution is dilute(e.g., less than about 3% by weight macrocyclic oligoester). A linearpolyester depolymerization reaction product solution (i.e., the inputsolution) 110 is pumped into a rising film evaporator 111. Some of thesolvent in the solution transitions into the vapor phase as it travelsup the rising film evaporator 111 and it then travels though a flashdevice 115. The solution then is pumped into a second rising filmevaporator 121. Thereafter the solution travels through another flashdevice 125. The solution that exits the flash device 125 travels alongpath 135 and has a higher macrocyclic oligoester concentration (e.g., anincrease from about 1% to about 3%). The vapor phase solvent that isremoved from flash devices 115 and 125 travels along paths 120′ and120″, is condensed in condensers 152 and 154, and is collected in aliquid receiver 127. The macrocyclic oligoester solution that exits theflash device 125 then travels along path 135 to a filter 141, whichremoves any remaining linear polyester and/or catalyst from thedepolymerization reaction product solution. The filter 141 may be, forexample, a Niagara filter or a Sparkler filter. A Niagara filter is amultiple tray filter available from Baker Hughes Corporation (Houston,Tex.). Similarly, a Sparkler filter is a multiple tray filter apparatusavailable from Sparkler Filters, Inc. (Conroe, Tex.). In one embodiment,a centrifuge is employed alternatively or in addition to the filter 141.A resulting output solution 190 exiting filter 141 may become the inputsolution in the next solvent removal step.

[0064] The output solution 190 may have a macrocyclic oliogesterconcentration of about 3%. In one embodiment, the rising film evaporator111 is held at a temperature between about 180° C.-185° C. atatmospheric pressure. In another embodiment, the rising film evaporator121 is held at temperature between about 180° C.-185° C. at atmosphericpressure. In other embodiments, each rising film evaporator 111 and 121is held at a temperature between about 120° C. to 280° C. at a pressureranging from about 0.001 torr to about atmospheric pressure.

[0065] Referring again to FIG. 1, when the concentration of macrocyclicoligomer input solution 10 is about 3%, two additional rising filmevaporators (not shown) may be placed in series between the first risingfilm evaporator 11 and the second rising film evaporator 21. The twoadditional rising film evaporators may employ similar conditions as thefirst rising film evaporator 11 and use steam to heat the macrocyclicoligomer and the solvent (e.g., at about 150° C. under a pressure ofabout 100 torr).

[0066] In one embodiment, the rising film evaporator employs steam toheat the solution to a temperature between about 120° C. to 200° C. Inyet another embodiment, the rising film evaporator employs hot oil toheat the solution to between about 200° C. to about 280° C. The risingfilm evaporators may be operated at pressures ranging from about 0.001torr to about atmospheric pressure. In one embodiment, between about 80%and about 90% of the solvent in the input solution is removed by eachrising film evaporator. Where the input solution has a relatively lowconcentration of macrocyclic oligoester, multiple rising filmevaporators may be employed in multiple steps. In one embodiment,multiple solvent removal apparatus are employed to achieve the desireddryness in the macrocyclic oligoester substantially free from solvent.

[0067]FIG. 3 schematically illustrates another embodiment of a solventremoval system 3. The system shown in FIG. 3 may be used alone or incombination with that of FIG. 2. An input solution 210 is pumped into afirst rising film evaporator 211. Thereafter, the solution travelsthrough a first flash device 255. Condenser 252 captures the vaporizedsolvent that is removed in the first rising film evaporator 211 and thefirst flash device 255. The solution then travels through a secondrising film evaporator 221 to a second flash device 265. Condenser 254captures the vaporized solvent that is removed in the second rising filmevaporator 221 and the second flash device 265. The solution thentravels through a third rising film evaporator 231. Subsequently, thesolution travels through a third flash device 275. Condenser 256captures the vaporized solvent that is removed in the third rising filmevaporator 231 and the third flash device 275. After traveling throughthe third flash device 275, the solution travels through the fallingfilm stripper 241. A macrocyclic oligoester output product 230substantially free from solvent is pumped out of the falling filmstripper 241. In one embodiment, the macrocyclic oligoester 230 is in amolten state. The vaporized solvent that is removed from flash device255, 265, and 275 travels along paths 220′, 220″, and 220′″ and iscondensed in condensers 252, 254 and 256, and is collected in the liquidreceiver 227.

[0068] In another embodiment, the first rising film evaporator has about20 square feet of evaporation surface area and is maintained at aboutatmospheric pressure and a temperature of about 185° C. The secondrising film evaporator has about 5 square feet of evaporation surfacearea and is maintained at a pressure of about 1 torr and at atemperature ranging between about 185° C. and about 190° C. The thirdrising film evaporator has about 1 square foot of evaporation surfacearea and is maintained at a pressure of about 1 torr and at atemperature ranging between about 185° C. and about 190° C. In thisembodiment, the first rising film evaporator, having a relatively largeevaporation surface area and being run at atmospheric pressure,typically removes the bulk of solvent from the input solution.

[0069] Generally and in one embodiment of the invention, solvent isremoved from an input solution of a macrocyclic oligoester by exposingthe input solution to an elevated temperature and a reduced pressure ina first short path evaporator. A short path evaporator is used tovaporize part or all of the solvent from a solution. A short pathevaporator can operate at a low pressure because the condenser islocated inside of the evaporator. The input solution may then travel toa second short path evaporator where it is exposed to an elevatedtemperature and a reduced pressure.

[0070]FIG. 4 schematically illustrates another embodiment of a solventremoval system 4. An input solution 310 of a 3% by weight macrocyclicoligoester solution is pumped into the top of a falling film stripper341. Thereafter, the solution travels through a flash device 315. Thesolvent that is vaporized in the falling film stripper 341 and the firstflash device 315 travels through a path 320′ to a condenser 352, and isremoved from the solution. The solvent that has traveled through thecondenser 352 is transported to a liquid receiver 327. The solutiontravels to the short path evaporator 311. In the short path evaporator311 the solution is exposed to an elevated temperature and reducedpressure. The solvent that is vaporized in the short path evaporator 311is condensed within the short path evaporator 311 and removed from thesolution. The solvent removed within the short path evaporator 311 istransported through a path 320″ to a liquid receiver 327. A macrocyclicoligoester output product 330 substantially free from solvent exits theshort path evaporator 311. In one embodiment, the macrocyclic oligoester330 is in a molten state. A macrocyclic oligoester substantially freefrom solvent is collected from the short path evaporator 311.

[0071] In one exemplary embodiment the input solution 310 of macrocyclicoligoester is heated to a temperature of about 180° C. and is pumpedinto the top of the falling film stripper 341 at a rate of about 5900kg/hr. The falling film stripper 341 is maintained at a temperature ofabout 180° C. and at about atmospheric pressure. The solution exits thebottom of the falling film stripper 341 at a temperature of about 180°C. The solution enters the flash device 315, which is held atatmospheric pressure and at a temperature of about 180° C. The solutionexiting the flash device 315 that enters the short path evaporator 311is at a temperature of about 180° C. The short path evaporator 311 has2.4 m² of surface area, is held at a temperature of about 210° C. and ata pressure of about 5 torr. The macrocyclic oligoester output product330 exits the short path evaporator 311 at a rate of about 181 kg/hr andat a temperature of about 210° C. The output product 330 contains lessthan 100 ppm of solvent. A suitable falling film stripper 341, flashdevice 315, and short path evaporator 311 that may be employed inaccordance with this exemplary embodiment are available from InconProcessing Technology (Batavia, Ill.).

[0072] In one embodiment, a compressor may be employed in place of acondenser. In another embodiment, the compressed gas or the condensedgas exiting the compressor or the condenser, respectively, may beemployed as the heat input to one or more of the stripping apparatusand/or the evaporating apparatus. For example, where a shell and tubeheat exchanger is employed, the compressed gas exiting a compressor maybe fed to the shell side of the heat exchanger.

[0073] Generally, where short path evaporators have been employed in thesolvent removal process, a sparger may not be necessary to obtain amacrocyclic oligoester substantially free from solvent. Short pathevaporators can operate effectively under lower vacuum and at lowertemperature conditions, thereby potentially saving energy costs. Also,the time required by the sparging step and the cost of maintainingsparging equipment are avoided when short path evaporators are employed.

[0074] Systems, apparatus, and equipment that may be employed or adaptedto perform the processes described herein are commercially available,for example, from Artisan Industries Inc. of Waltham, Mass. and from LCIof Charlotte, N.C. Suitable rising film evaporators include heatexchangers available from Troy Boiler (Albany, N.Y.). Suitable fallingfilm strippers, condensers and flash devices may be supplied by ArtisanIndustries Inc. (Waltham, Mass.) and Incon Processing Technology(Batavia, Ill.). Suitable short path evaporators are available fromIncon Processing Technology Batavia, Ill.). Suitable liquid receiversare available from suppliers including, Artisan Industries Inc.(Waltham, Mass.) and Incon Processing Technology (Batavia, Ill.)

[0075] Shaping Macrocyclic Oligoesters

[0076] In another aspect, the invention features a process for shaping apartially-crystallized macrocyclic oligoester. This process includesproviding a substantially solvent-free molten macrocyclic oligoester.The substantially solvent-free molten macrocyclic oligoester is shearedto form a partially-crystallized macrocyclic oligoester, which can beshaped.

[0077] In one embodiment, the substantially solvent-free moltenmacrocyclic oligoester is continuously sheared to form apartially-crystallized macrocyclic oligoester. In another embodiment,shaping of the partially-crystallized macrocyclic oligoester iscontinuous. In yet another embodiment, the molten macrocyclic oligoesteris continuously sheared and the partially-crystallized macrocyclicoligoester is continuously shaped.

[0078] Once substantially free from solvent the macrocyclic oligoester,which may be a molten liquid at the solvent-removal temperature, iscooled and solidified into a usable form. When molten macrocyclicoligoester (such as macrocyclic (1,4-butylene terephthalate)) is cooledquickly, it is typically amorphous. In its amorphous state, themacrocyclic oligoester is sticky and “droplets” tend to agglomerate intoa large mass. Amorphous macrocyclic oligoester also absorbs water fromthe atmosphere, which can be detrimental to subsequent processing.

[0079] Shear-induced partial-crystallization is used to facilitatecrystallization of the macrocyclic oligoester. According to embodimentsof the invention, an extruder, a scraped surface crystallizer, and/or ashear mixer are employed to partially-crystallize the product to form apartially-crystallized macrocyclic oligoester. A shear mixer includesany crystallizer that facilities crystallization by shear mixing. Theextruder may be employed to extrude the macrocyclic oligoester at atemperature below the melting point of the macrocyclic oligoester,thereby forming a partially-crystallized macrocyclic oligoester.Shearing may include shearing, cooling, or shearing and coolingsimultaneously.

[0080] Suitable product forms (e.g., pellets, pastilles, flakes, andprepregs) that are stable in the environment and easy to handle may beobtained by these methods. The partially-crystallized macrocyclicoligoester then may be collected. The collection may be continuouslyperformed depending on the application.

[0081] Two or more processes of the invention may be carried outsimultaneously. In one embodiment, an extruder removes solvent from thesolution of macrocyclic oligoester to form a substantially solvent-freemolten macrocyclic oligoester that the extruder shears to form apartially-crystallized macrocyclic oligoester that is shaped into apellet

[0082] The macrocyclic oligoester may be sheared at a temperature thatis lower than the melting point of the macrocyclic oligoester. In oneembodiment, the shearing step is conducted at a temperature betweenabout 100° C. and about 165° C. In another embodiment, the shearing stepis conducted at a temperature between about 145° C. and about 155° C.

[0083] Additionally, one or more of various additives and fillers can beincorporated into the macrocyclic oligoester, before, during or aftersolvent removal to yield a fully formulated product. For example, in themanufacture of an article, various types of fillers may be included.Filler often is included to achieve a desired property, and may bepresent in the resulting polyester polymer. The filler may be present toprovide stability, such as chemical, thermal or light stability, to theblend material or the polyester polymer product, and/or to increase thestrength of the polyester polymer product. A filler also may provide orreduce color, provide weight or bulk to achieve a particular density,provide flame resistance (i.e., be a flame retardant), be a substitutefor a more expensive material, facilitate processing, and/or provideother desirable properties as recognized by a skilled artisan.

[0084] Illustrative examples of fillers are, among others, fumedsilicate, titanium dioxide, calcium carbonate, chopped fibers, fly ash,glass microspheres, micro-balloons, crushed stone, nanoclay, linearpolymers, and monomers. One or more fillers may be added before, during,or after the polymerization reaction between a macrocyclic oligoesterand a cyclic ester. For example, fillers may be added to a substantiallysolvent-free macrocyclic oligoester. Optionally the filler may be addedwhen the substantially solvent-free macrocyclic oligoester is in moltenform. Also, fillers can be used to prepare polyester polymer composites.

[0085] In some embodiments, additional components (e.g., additives) areadded to the macrocyclic oligoesters. Illustrative additives includecolorants, pigments, magnetic materials, anti-oxidants, UV stabilizers,plasticizers, fire-retardants, lubricants, and mold releases. In otherembodiments, one or more catalysts are added to the macrocyclicoligoester. Exemplary catalysts that may employed in accordance with theinvention are described below.

[0086] Formulating Macrocyclic Oligoesters

[0087] In another aspect, the invention features processes forformulating macrocyclic oligoesters and processes for making prepregsfrom macrocyclic oligoesters and polymerization catalysts.

[0088] In one embodiment, a mixture of a molten macrocyclic oligoesterand a polymerization catalyst substantially free from solvent isprovided. The mixture of the molten macrocyclic oligoester andpolymerization catalyst is deposited onto a fabric material to form aprepreg. In one embodiment, the molten macrocyclic oligoester andpolymerization catalyst are partially-crystallized prior to beingdeposited onto the fabric material.

[0089] A mixture of a molten macrocyclic oligoester and a polymerizationcatalyst substantially free from solvent may be continuously provided.The mixture of the macrocyclic oligoester and the polymerizationcatalyst may be partially crystallized. In one embodiment, the mixtureis continuously partially crystallized. The partially-crystallizedmixture of the macrocyclic oligoester and the polymerization catalystthen may be deposited onto a fabric material. In another embodiment, thepartially-crystallized mixture is continuously deposited onto a fabricmaterial.

[0090] In other embodiments, a macrocyclic oligoester (e.g., pellets) isfed to a hot mixing device (e.g., an extruder or a Readco mixer) withother solid or liquid additives (e.g., stabilizers or polymerizationcatalysts) with or without fillers. The mixing device partially meltsthe macrocyclic oligoester into a paste to enhance mixing and flow. Theformulated product, which remains partially crystalline, then is formedinto shapes such as pellets, flakes, pastilles, and/or applied directlyto a fabric material to male a prepreg. This method typically avoids theproblems of handling amorphous macrocyclic oligoester.

[0091] In yet other embodiments, the partially-crystallized mixture ofmolten macrocyclic oligoester and polymerization catalyst is depositedonto a fabric material. In certain embodiments the molten macrocyclicoligoester and polymerization catalyst are shear mixed in a shear mixer;alternatively, they may be processed in an extruder. The shear-mixingmay be conducted at a temperature between about 145° C. and about 155°C. The fabric material(s) may be selected from the group of fiber tow,fiber web, fiber mat, felt, non-woven material, and random and wovenmaterial.

[0092] Prior to partial-crystallization, the molten macrocyclicoligoester may contain less than about 200 ppm of solvent Preferably,the molten macrocyclic oligoester contains less than about 100 ppm ofsolvent. More preferably, the molten macrocyclic oligoester containsless than about 50 ppm of solvent or less than about 10 ppm of solvent

[0093] The partially-crystallized mixture of the macrocyclic oligoesterand the polymerization catalyst may be deposited onto the fabricmaterial in a pre-selected array. In addition, the fabric materialhaving the mixture of macrocyclic oligoester and polymerization catalystdeposited thereon may be formed into a desired shape, for example, anautobody panel shape. One or more additives may be added to the moltenmacrocyclic oligoester. Exemplary additives may be selected from thegroup of colorants, pigments, magnetic materials, anti-oxidants, UVstabilizers, plasticizers, fire-retardants, lubricants, and moldreleases.

[0094] In one embodiment, the molten macrocyclic oligoester andpolymerization catalyst are partially-crystallized prior to beingdeposited onto the fabric material. The mixture of molton macrocyclicoligoester and polymerization catalyst may be partially-crystallized by,for example, shear mixing. In certain embodiments, shear mixing isconducted within a temperature range between about 145° C. and about155° C. In other embodiments the mixture of molton macrocyclicoligoester and polymerization catalyst is partially-crystallized byextrusion, which is often conducted within a temperature range betweenabout 145° C. and about 155° C.

[0095] The partially-crystallized mixture of macrocyclic oligoester andpolymerization catalyst may be deposited onto the fabric material indiscrete droplets of a selected size according to a pattern of apre-selected array. In certain embodiments, the molten macrocyclicoligoester is mixed with one or more additive(s) and/or filler(s). Thefabric material may be selected from the group of fiber tow, fiber web,fiber mat, felt, non-woven material, random, and woven material. Thefabric material employed in a prepreg may vary depending on the end useapplication of the prepreg. Also, the fiber used to make the fibermaterial, or any fiber sizing agents or other agents present on thefiber material, may impact the suitability of the fiber material for usein a prepreg. For example, some catalysts and/or macrocyclic oligoesterand polymerization catalyst mixtures may interact with the fibers and/orany sizing or other agents that are present on the fabric material.

[0096] In some embodiments, the partial crystallization step occurscontinuously. In other embodiments, the partially-crystallized mixtureof macrocyclic oligoester and the polymerization catalyst iscontinuously deposited on the fabric material. In still otherembodiments, the process of malting the prepreg is continuous wherebythe mixture of a molten macrocyclic oligoester and a polymerizationcatalyst, which is substantially free from solvent, is continuouslyprovided, continuously partially-crystallized, then continuouslydeposited onto a fabric material.

[0097] In another embodiments, the process of solvent removal and theprocess of prepreg formation are combined, creating a continuous processfrom the feed solution of a macrocyclic oligoester to formation ofprepregs of macrocyclic oligoester substantially free from the solvent.The prepregs may contain one or more additives and a polymerizationcatalyst. Such continuous processes may provide advantages in manyaspects such as in reducing energy cost and processing time andoptimizing equipment usage.

[0098]FIG. 5 schematically illustrates one embodiment of a process 5 formaking pellets from a molten product with an underwater pelletizer. Inthis embodiment, a molten macrocyclic oligoester 530, which issubstantially free from solvent, is fed into a shear mixer 360. Theshear mixer 360 is connected to a temperature control loop (not shown).The shear mixer 360 may be a Readco mixer (York, Pa.), which is like atwin screw extruder, but less heavy duty. The molten macrocyclicoligoester within the shear mixer 360 is typically cooled to atemperature between about 80° C. and about 140° C., preferably betweenabout 130° C. and about 140° C. By lowering the temperature in the shearmixer 360, the macrocyclic oligomer is crystallized partially and ispaste-like. Generally, the partially-crystallized macrocyclic oligomeremployed to make pellets 435 measures between about 3000 cp.(centipoise) and about 5000 cp., which typically indicates that about30% of the macrocyclic oligomer is crystallized.

[0099] The partially-crystallized macrocyclic oligomer travels from theshear mixer 360 to a diverter valve 365. The diverter valve 365 may beused to divert the product from the process to, for example, a bucketwhen the pelletizer starts up. The diverter 365 typically is used toensure that the partially-crystallized macrocyclic oligoester istraveling to the upstream cutter 370 at a minimum velocity. A suitablediverter 365 and a suitable cutter 370 may be available from GalaIndustries Eagle Rock, Va.), Incon Processing Technology (Batavia,Ill.), and/or Artisan Industries Inc. (Waltham, Mass.). After a minimumvelocity is achieved, the partially-crystallized macrocyclic oligomertravels to the cutter 370. At the cutter 370, the partially-crystallizedpaste-like macrocyclic oligomer is cut into the shape of pellets in aslurry of water. One or more pellets may be cut by the cutter 370 atonce. The pellets are then removed from the slurry of water into aseparator 380. The separator 380 may be a screen, which may be a movingbelt. A suitable separator 380 may be available from Gala Industries(Eagle Rock, Va.), Incon Processing Technology (Batavia, Ill.), and/orArtisan Industries Inc. (Waltham, Mass.). Subsequently, the pellets 435are dried in a dryer 385 and then transferred to a pellet hopper 395 anda packager 550. The dryer 385 may be a fluid bed dryer available fromKason Corporation (Milburn, N.J.). A suitable pellet hopper 395 and asuitable packager 550 may be available from Gala Industries (Eagle Rock,Va.), Incon Processing Technology (Batavia, Ill.), and/or ArtisanIndustries Inc. (Waltham, Mass.). As depicted, the water that wasseparated from the pellets is recycled through a sump 384 and a watercirculation pump 388. A suitable sump 384 and a suitable circulationpump 388 may be available from Gala Industries (Eagle Rock, Va.), InconProcessing Technology (Batavia, Ill.), and/or Artisan Industries Inc.(Waltham, Mass.).

[0100]FIG. 6 schematically illustrates an embodiment of a process 6 formaking either prepreg or pastille from a molten product utilizing apastillation process. A molten macrocyclic oligoester 630, which issubstantially free from solvent, is fed into a shear mixer 360 that isconnected to a temperature control loop (not shown) to control thetemperature of the shear mixer 360. The molten macrocyclic oligomerwithin the shear mixer 360 is typically cooled to a temperature betweenabout 80° C. and about 140° C., preferably between about 130° C. andabout 140° C.

[0101] In certain embodiments, the temperature control loop maintainsthe shear mixer 360 at a temperature of about 100° C. In otherembodiments, the shear mixer 360 is an extruder. In yet otherembodiments, the shear mixer 360 is a Readco mixer (York, Pa.), which islike a twin screw extruder, but less heavy duty.

[0102] By lowering the temperature in the shear mixer, the macrocyclicoligomer is partially crystallized and becomes paste-like. Thetemperature and/or the level of shear provided to produce the paste-likemacrocyclic oligomer varies according to the composition of themacrocyclic oligomer, including the presence of any additives.Generally, the partially-crystallized macrocyclic oligomer employed tomake pastilles measures between about 500 cp. and about 1000 cp., whichtypically indicates that it is between about 15% and about 20%crystallized. The molten macrocyclic oligomer may contain some residualsolvent (e.g., between about 100 ppm and about 10 ppm) as the moltenresin enters the shaping process at a temperature between about 150° C.and about 200° C.

[0103] Both prepregs and pastilles can be made from thepartially-crystallized and paste-like macrocyclic oligomer utilizingpastillation equipment. The partially-crystallized paste-likemacrocyclic oligomer travels from the shear mixer 360 and enters adroplet generator 390. The droplet generator 390 is employed to makedesired sized droplets of macrocyclic oligoester. In one embodiment, aSandvik Rotoformer available from Sandvik Process Systems of Totowa,N.J. is employed to make droplets. When pastilles 425 are manufactured,the droplet generator 390 may drop pastilles 325 directly onto a movingbelt 500.

[0104] The moving belt 500 may be of any length and size and istypically between about 50 feet to about 100 feet in length The bottomside of the moving belt 500 may be cooled, for example, by providingwater underneath the moving belt 500. The length of the moving belt 500and the cooling method can be selected to cool the pastilles 425 beforethe end of the moving belt 500. In some embodiments, a scraping bar (notshown) is employed at the end of the moving belt 500 to remove thepastilles 425 from the moving belt 500. In one embodiment, a moving belt500 available from Sandvik Process Systems of Totowa, N.J. is employed.

[0105] When a prepreg 445 is manufactured, the droplet generator 390 maydrop the material 415 (e.g., macrocyclic oligoester plus apolymerization catalyst) onto a fabric material 600 that is fed onto themoving belt 500. The length of the moving belt 500 and any coolingmethod will be selected to cool the material 415 into the fabricmaterial 600, forming the prepreg 445.

[0106] In some embodiments, an underwater pelletizer is used for makingpellets. In For example, a Gala type underwater pelletizer (availablefrom Gala Industries, Inc. of Eagle Rock, Va.) may be used for makingpellets. Alternatively, a pastillator may be used for forming pastilles.For example, a Sandvik Rotoformer (available from Sandvik ProcessSystems of Totowa, N.J.) may be used to form pastilles.

[0107] In yet another aspect of the invention, the process of solventremoval and the process of shaping a partially-crystallized macrocyclicoligoester are combined, creating a continuous process from feeding asolution of a macrocyclic oligoester to shaping the macrocyclicoligoester. For example, in one embodiment, the process of solventremoval and the process of pastillation may be combined, therebycreating a continuous process from input solution of a macrocyclicoligoester to pastilles of macrocyclic oligoester substantially freefrom the solvent. In one embodiment, a solution of macrocyclicoligoester is provided. During the solvent removal process, thetemperature often is elevated to between about 180° C. and about 200°C., and the pressure maintained between about atmospheric pressure andabout 10 torr. In these embodiments, the solvent is continuously removedto produce a substantially solvent-free molten macrocyclic oligoester.

[0108] The substantially solvent-free molten macrocyclic oligoester maybe sheared at a temperature below the melting point of the moltenmacrocyclic oligoester to form a partially-crystallized macrocyclicoligoester. The shearing temperature may be maintained at, for example,between about 145° C. and about 155° C. Subsequently, thepartially-crystallized macrocyclic oligoester may be formed into anydesirable shapes including pellets, pastilles, and flakes.

[0109] Additives and fillers may be formulated with a macrocyclicoligoester or with a mixture of a macrocyclic oligoester and a catalyst.In one embodiment, the additive(s) and/or filler(s) are formulated witha macrocyclic oligoester while the latter macrocyclic oligoester iscompletely molten. In other embodiments, the additive(s) and/orfiller(s) are formulated with a macrocyclic oligoester while the lattermacrocyclic oligoester is partially molten and partially crystalline. Inyet other embodiments, the additive(s) and/or filler(s) are formulatedwith a macrocyclic oligoester while the macrocyclic oligoester iscompletely crystalline. The formulated macrocyclic oligoester isprepared into a prepreg in the form of pastilles on a fabric material.

[0110] Pastille prepregs may be prepared from a blend material thatincludes macrocyclic oligoesters. In one embodiment, the inventionrelates to methods for preparing pastille thermoplastic prepregs basedon a blend material that includes at least one macrocyclic oligoesterand at least one polymerization catalyst.

[0111] Thermoplastic prepregs typically have been produced with theresin close to the fiber. If the melt viscosity of the resin is high,the resin needs to be close to the fiber in order to wet-out the fiberproperly. This typically is the case with thermoplastic prepregs madeusing a hot melt method with thermoplastic powder, co-mingled tows ofreinforcing fiber and thermoplastic fiber, or co-woven fabrics. Thesematerials require a process which often includes three steps: 1) heatingand melting the resin, 2) wetting out of the fiber and consolidating,and 3) cooling down and solidifying.

[0112] Macrocyclic oligoesters, as discussed above, melt to a lowviscosity that may be many orders of magnitude lower than the viscosityof conventional thermoplastics. Thus, combining and wetting-out ofmacrocyclic oligoesters (when melted) with fillers and/or reinforcingfibers during the heating cycle of a process can be done much moreeasily than conventional thermoplastics. Hence, in prepreg fabrics madewith macrocyclic oligoesters, the resin does not need to be distributedas close to the fiber (i.e., each and every fiber) as is needed forconventional thermoplastics. That is, resin can be placed at discretelocations, but melt and flow to wet-out the entire fabric when the resinis melted.

[0113] When a prepreg is made with a blend material that includes amacrocyclic oligoester, the blend material can be a one-partready-to-use system with a catalyst already included. FIG. 7 illustratesone embodiment of the invention, a process 7 for making a prepreg 445from a macrocyclic oligoester or a blend material of macrocyclicoligoester with one or more other components such as a polymerizationcatalyst. The process allows the making of a prepreg 445 that has thedesired resin and fabric material in a pre-selected ratio. Such prepregscan simplify upstream processes employing prepregs.

[0114] Referring to FIG. 7, a blend material (e.g., a one-part system)is melted and applied to a reinforcing fabric 600 in discreet resindrops 415 and then cooled before significant polymerization takes place.The molten resin 505 is pumped into a channel in the bottom of arotating cylinder 510 and comes out through the holes 507 in thecylinder each time the holes 507 line up with the channel. In oneembodiment, a rotating cylinder 510 available from Sandvik ProcessSystems of Totowa, N.J. is employed in the process. Consequently, liquiddrops of resin fall at predetermined intervals onto a moving belt 500(e.g., a steel belt). These discrete resin drops 415 can be arranged ina pre-selected array (e.g., a pattern) so that the amount of resin isuniform per unit fabric area (if uniformity is desired) and is of adesired value. In one embodiment, the amount of resin per unit fabricarea ranges from about 3% by weight resin to about 97% by weight resin.In another embodiment, the amount of resin per unit fabric area rangesfrom about 30% by weight resin to about 80% by weight resin.

[0115] The amount, pattern, and spacing of the dropped resin determinethe “average” ratio of fabric material to resin before the resin ismelted and distributed throughout the fabric material. There is nolimitation as to the amount and pattern of the resin drops as long asthe desired preregs are formed. The ratio of fabric material to resinmay be uniform or varied across the prepreg and can be manipulated bycontrolling the size of each drop of resin and the space between them.

[0116]FIG. 8 illustrates a schematic flow diagram of an embodiment of asolvent removal system where the solvent removal system 1 illustrated inFIG. 2 is linked with the solvent removal system 2 illustrated inFIG. 1. According to this embodiment, which is typically employed wherethe linear polyester depolymerization reaction product solution (i.e.,the input solution) is a dilute (e.g., about 1% by weight macrocyclicoligoester), input solution 110 is first processed though system 1 toyield a resulting output solution 190. The solution 190 that is theproduct of system 1 typically contains about 3% by weight macrocyclicoligoester. The solution 190 enters system 2 as input solution 10. Theinput solution 10 is processed thorough system 2 to yield an outputproduct 130 substantially free from solvent.

[0117]FIG. 9 is a schematic flow diagram of an embodiment of a systemfor shaping macrocyclic oligoesters from a solution of macrocyclicoligoester and solvent According to this embodiment, the linked solventremoval systems 1 and 2, described above, are further linked to theprocess 5 for making pellets from a molten product illustrated in FIG.5. The input solution 110 is a dilute solution (e.g., about 1% by weightmacrocyclic oligoester) which is first processed though system 1 toyield a resulting output solution 190. The solution 190 that is theproduct of system 1 typically contains about 3% by weight macrocyclicoligoester. Solution 190 enters system 2 as input solution 10 and isprocessed thorough system 2 to yield an output product 130 substantiallyfree from solvent. The output product 130 may be molten. Output product130 enters process 5 as molten macrocyclic oligoester 530, which isprocessed through system 5 to yield pellet 435.

[0118]FIG. 10 is a schematic flow diagram of an embodiment of a systemfor shaping macrocyclic oligoesters from a solution of macrocyclicoligoester and solvent. According to this embodiment, the solventremoval system 2 is linked to the process 5, described above, which makepellets from a molten product. According to this embodiment, the inputsolution 10 containing about 3% by weight macrocyclic oligoester isprocessed thorough system 2 to yield an output product 130 substantiallyfree from solvent. In one embodiment, the output product 130 is molten.Output product 130 enters system 5 as molten macrocyclic oligoester 530,which is processed through system 5 to yield pellet 435.

[0119] Just as the processes in FIG. 8-10 can be linked to provideincreased benefits, in other variations of such embodiments (not shown),alternative solvent removal system(s), for example, systems 1, 2, 3, and4, described above with reference to FIGS. 1-4, may be linked to oneanother and/or to processes for shaping macrocyclic oligoesters from asolution of macrocyclic oligoester and solvent, such as, for example,processes 5, 6, and 7, described above with reference to FIGS. 5-7. Forexample, referring again to FIG. 8, FIG. 9, and FIG. 10 the solventremoval system 2 can be replaced by system 3 (FIG. 3) or system 4 (FIG.4). Referring still to FIG. 9, and FIG. 10, the shaping process 5 can bereplaced by process 6 (FIG. 6).

[0120] The advantages of the above systems, processes and productprepregs include the ability to “drape” easily into a mold, the abilityto flex without cracking and crumbling the resin drops, and the abilityto use conventional pastillation equipment. Also, instead of placing thepellets on a conveyor belt, they are placed on a reinforcing fabric. Inaddition, the processes can be conducted isothermally (i.e. at constanttemperature) and in a vacuum bag or in a compression molding press.

[0121] Catalysts may be formulated with macrocyclic oligoesters toprepare prepregs. Catalysts may be part of a blend material ofmacrocyclic oligoesters, see U.S. Pat. No. 6,369,157, the entirecontents of which is incorporated by reference herein, or may be addedbefore or during the formulation processes described herein. Catalyststhat may be employed in the invention include those that are capable ofcatalyzing a transesterification polymerization of a macrocyclicoligoester. As with state-of-the-art processes for polymerizingmacrocyclic oligoesters, organotin, and organotitanate compounds are thepreferred catalysts, although other catalysts may be used. Detaileddescription of polymerization catalysts can be found in commonlyassigned U.S. Ser. No. 09/754,943 entitled “Macrocyclic PolyesterOligomers and Processes for Polymerizing the Same” by Winckler et al.,U.S. Ser. No. 10/102,162 entitled “Catalytic Systems” by Wang, and U.S.Ser. No. 10/040,530 entitled “Polymer-Containing Organo-Metal Catalysts”by Wang, the entire contents of which are incorporated by referenceherein.

[0122] Illustrative examples of classes of tin compounds that may beused in the invention includes monoalkyltin(IV) hydroxide oxides,monoalkyltin(IV) chloride dihydroxides, dialkyltin(IV) oxides,bistrialkyltin(IV) oxides, monoalkyltin(IV) trisalkoxides,dialkyltin(IV) dialkoxides, trialkyltin(IV) alkoxides, tin compoundshaving the formula (II):

[0123] and tin compounds having the formula (III):

[0124] wherein R₂ is a C₁₋₄ primary alkyl group, and R₃ is C₁₋₁₀ alkylgroup.

[0125] Specific examples of organotin compounds that may be used in thisinvention include dibutyltin dioxide,1,1,6,6-tetra-n-butyl-1,6-distanna-2,5,7,10-tetraoxacyclodecane,n-butyltin(IV) chloride dihydroxide, di-n-butyltin(IV) oxide, dibutyltindioxide, di-n-octyltin oxide, n-butyltin tri-n-butoxide,di-n-butyltin(IV) di-n-butoxide,2,2-di-n-butyl-2-stanna-1,3-dioxacycloheptane, and tributyltin ethoxide.See, e.g., U.S. Pat. No. 5,348,985 to Pearce et al. In addition, tincatalysts described in commonly owned U.S. Ser. No. 09/754,943(incorporated herein by reference in its entirety) may be used in thepolymerization reaction.

[0126] Titanate compounds that may be used in the invention includetitanate compounds described in commonly owned U.S. Ser. No. 09/754,943.Illustrative examples include tetraalkyl titanates (e.g.,tetra(2-ethylhexyl) titanate, tetraisopropyl titanate, and tetrabutyltitanate), isopropyl titanate, titanate tetraalkoxide. Otherillustrative examples include (a) titanate compounds having the formula(IV):

[0127] wherein each R₄ is independently an alkyl group, or the two R₄groups taken together form a divalent aliphatic hydrocarbon group; R₅ isa C₂₋₁₀ divalent or trivalent aliphatic hydrocarbon group; R₆ is amethylene or ethylene group; and n is 0 or 1,

[0128] (b) titanate ester compounds having at least one moiety of theformula (V):

[0129] wherein each R₇ is independently a C₂₋₃ alkylene group; Z is O orN; R₈ is a C₁₋₆ alkyl group or unsubstituted or substituted phenylgroup; provided when Z is O, m=n=0, and when Z is N, m=0 or 1 and m+n=1,and

[0130] (c) titanate ester compounds having at least one moiety of theformula (VI):

[0131] wherein each R₉ is independently a C₂₋₆ alkylene group; and q is0 or 1.

[0132] The compositions and methods of the invention may be used tomanufacture articles of various size and shape from various macrocyclicoligoesters. Exemplary articles that may be manufactured by theinvention include without limitation automotive body panels and chassiscomponents, bumper beams, aircraft wing skins, windmill blades, fluidstorage tanks, tractor fenders, tennis rackets, golf shafts, windsurfingmasts, toys, rods, tubes, bars stock, bicycle forks, and machinehousings.

EXAMPLES

[0133] The following examples are provided to further illustrate and tofacilitate the understanding of the invention. These specific examplesare intended to be illustrative of the invention.

Example A

[0134] The macrocyclic oligoesters used in the following examples arethe macrocyclic oligoesters of 1,4-butylene terephthalate. Themacrocyclic oligoesters were prepared by heating a mixture of polyesterlinears, organic solvents, such as o-xylene and o-dichlorobenzene, whichare substantially free from oxygen and water, and tin or titaniumcompounds as transesterification catalysts. See U.S. Pat. No. 5,668,186(incorporated herein by reference in its entirety).

Example 1 Preparation of Macrocyclic (1,4-butylene terephthalate)Oligomer Pellets

[0135] Macrocyclic (1,4-butylene terephthalate) oligoester powder wasfed at a rate of about 9 kg/hr through an extruder at about 120° C. tomelt into a paste and processed at a rate of about 9 kg/hr through aGala underwater pelletizer available from Gala Industries (Eagle Rock,Va.). No die freeze off was observed. The material cut cleanly on thedie face. The pellets were strained out of the water and air dried tocontain 80 ppm or less of water.

Example 2 Macrocyclic (1,4-butylene terephthalate) Oligomer Pastilles

[0136] Macrocyclic (1,4-butylene terephthalate) oligomer powdercontaining less than 1,000 ppm solvent was melted in a tank at about170° C. and fed at a rate of 60 kg/hr to a Sandvik Rotoformer to formpastilles. No partial-crystallization was used. The pastilles wereamorphous and agglomerated together. The macrocyclic (1,4-butyleneterephthalate) oligomer was pastilled smoothly into pastilles.

Example 3 Formulated Macrocyclic (1,4-butylene terephthalate) OligomerPastilles

[0137] Macrocyclic (1,4-butylene terephthalate) oligoester powder wasmelted and melt blended at a temperature between about 120° C. and about140° C. with additives including a polymerization catalyst (0.33% byweight FASTCAT 4101 (Atofina, Philadelphia, Pa.)) and thermalstabilizers (0.4% by Weight IRGANOX 1010 (Ciba Specialty ChemicalsCorporation, Tarrytown, N.Y.)). The formulated product was then fed at arate of about 45 kg/hr to the Sandvik Rotoformer to form pastilles, asin Example 2.

Example 4 Formulated Macrocyclic (1,4-butylene terephthalate) OligomerPastilles on Glass Mat

[0138] Macrocyclic (1,4-butylene terephthalate) oligoester powder wasmelt blended with catalyst (0.33% by weight FASTCAT 4101 catalyst) andstabilizers (0.4% by weight IRGANOX 1010) and pastilled onto glass matattached to the Sandvik Rotoformer belt. The Macrocyclic (1,4-butyleneterephthalate) oligoester contained less than 1000 ppm solvent. Theweight of macrocyclic (1,4-butylene terephthalate) oligoester depositedonto an area of glass mat was controlled to between about 400 g/m² toabout 800 g/m². The pastilles had a hemispherical shape and were about 7mm in diameter, the pastilles were spaced about 15 mm apart from oneanother. The glass mat prepreg was flexible, with good adhesion of themacrocyclic (1,4-butylene terephthalate) oligoester pastilles. Thisprepreg mat can be cured to crystallize the macrocyclic (1,4-butyleneterephthalate) oligoester to reduce moisture adsorption and tack. Theprepreg was polymerized at a temperature of about 190° C. to highmolecular weight polyester (about 80,000 Dalton).

Example 5 Solvent Removal via Stripping

[0139] A solution of macrocyclic (1,4-butylene terephthalate) oligoesterin o-dichlorobenzene was fed to an Artisan evaporative stripper fromArtisan Industries, Inc. (Waltham, Mass.) A two-stage flash evaporatorwas operated at a temperature ranging between about 180° C. and about220° C. and at a pressure ranging between about 10 torr and aboutatmospheric pressure to concentrate a 10% solution of macrocyclic(1,4-butylene terephthalate) oligomer to less than 100 ppmo-dichlorobenzene.

Example 6 Solvent Removal via Evaporation and Stripping

[0140] An input solution of 3% by weight macrocyclic (1,4-butyleneterephthalate) oligoester in o-dichlorobenzene solution was fed at arate of about 6,045 kg/hr into a series of rising film evaporators and afalling film stripper available from Artisan Industries, Inc. to producean output solution with solvent levels of less than 100 ppm at a rate ofabout 181 kg/hr.

[0141] In one embodiment, the input solution, having a temperature ofabout 65° C., is fed at a rate of about 6,045 kg/hr into a first risingfilm evaporator having an evaporation surface area of about 317 ft². Thefirst rising film evaporator is held at temperature of about 180° C. atatmospheric pressure. Thereafter, the solution exits the first risingfilm evaporator and enters a first flash device. The first flash deviceis held at temperature of about 180° C. at atmospheric pressure. A firstcondenser captures the vaporized solvent that is removed in the firstrising film evaporator and the first flash device.

[0142] The solution exits the first flash device and travels at atemperature of about 180° C. to a second rising film evaporator. Thesecond rising film evaporator has an evaporation surface area of about81 ft² and is held at a temperature of about 193° C. at atmosphericpressure. The solution exiting the second rising film evaporator has atemperature of about 193° C. and enters a second flash device. Thesecond flash device is held at a temperature of about 180° C. atatmospheric pressure. A second condenser captures the vaporized solventthat is removed in the second rising film evaporator and the secondflash device.

[0143] The solution exits the second flash device and travels to a thirdrising film evaporator. The third rising film evaporator has anevaporation surface area of about 21 ft² and is held at temperature ofabout 199° C. at atmospheric pressure. Thereafter, the solution exitsthe third rising film evaporator at a temperature of about 199° C. andenters a third flash device. The third flash device is held at atemperature of about 180° C. at atmospheric pressure. A third condensercaptures the vaporized solvent that is removed in the third rising filmevaporator and the third flash device.

[0144] The solution exits the third flash device and travels to a fourthrising film evaporator. The fourth rising film evaporator has anevaporation surface area of about 8 ft² and is held at temperature ofabout 204° C. at atmospheric pressure. Thereafter, the solution exitsthe fourth rising film evaporator at a temperature of about 204° C. andenters a fourth flash device. The fourth flash device is held at atemperature of about 180° C. at atmospheric pressure. A fourth condensercaptures the vaporized solvent that is removed in the fourth rising filmevaporator and the fourth flash device. Each of the four condensersemploy cooling water to condense the vaporized solvent and bring thecondensed solvent to a temperature of about 176° C.

[0145] The solution exits the fourth flash device and travels to a fifthrising film evaporator. The fifth rising film evaporator has anevaporation surface area of about 10 ft² and is held at temperature ofabout 226° C. at a pressure of about 1 torr. Thereafter, the solutionexits the fifth rising film evaporator at a temperature of about 226° C.and enters the top of a falling film stripper. The falling film stripperis held at a temperature of about 226° C. at a pressure of about 1 torr.A vacuum pump captures the vaporized solvent that is removed in thefalling film stripper and the fifth rising film evaporator. The vacuumpump is held at about 0.5 torr. The vaporized solvent travels from thevacuum pump to a fifth condenser. The fifth condenser is sized at 75 ft²and employs cooling water to condense the vaporized solvent and bringthe condensed solvent to a temperature of about 176° C.

[0146] Nitrogen from a nitrogen sparger is introduced to the solutiontraveling through the falling film stripper at a rate of about 9 kg/hr.After sparging, the macrocyclic oligoester product has a temperature ofabout 226° C. and contains less than 100 ppm solvent. The macrocyclicoligoester exits the process at a rate of about 181 kg/hr.

[0147] Alternatively, a single flash device or a single condenser isemployed in place of two or more of the flash devices and two or more ofthe condensers that are described. A single flash device may be employedin the place of the second, third, and fourth flash devices describedabove. A single flash device may house three distinct conduits for thesolutions exiting the second, third, and fourth rising film evaporators.Such a flash device may have three conduits that are adjacent to oneanother. The flash device may also be constructed so that the conduitfor the solution exiting the third rising film evaporator is placedinside the conduit for the solution exiting the second rising filmevaporator, and the conduit for the solution exiting the fourth risingfilm evaporator is placed inside the conduit for the solution exitingthe third rising film evaporator. A single condenser (e.g., a condenserwith a 500 ft² area) may be employed in the place of the second, third,and fourth condenser described above.

[0148] Each of the patent and patent application documents disclosedhereinabove are incorporated by reference herein in their entirety.

[0149] Variations, modifications, and other implementations of what isdescribed herein will occur to those of ordinary skill in the artwithout departing from the spirit and the scope of the invention asclaimed.

What is claimed is:
 1. A process for isolating a macrocyclic oligoester,the process comprising the steps of: (a) providing a solution comprisinga macrocyclic oligoester and a solvent, the macrocyclic oligoestercomprising a structural repeat unit of formula (1):

 wherein R is an alkylene, a cycloalkylene, or a mono- orpolyoxyalkylene group and A is a divalent aromatic or alicyclic group;(b) removing the solvent; and (c) collecting the macrocyclic oligoestersubstantially free from the solvent.
 2. The process of claim 1 whereinstep (b) comprises removing the solvent at an elevated temperature, at areduced pressure, or both.
 3. The process of claim 2 wherein step (b) isconducted within a temperature range of about ambient temperature toabout 300° C.
 4. The process of claim 3 wherein step (b) is conductedwithin a temperature range of about 180° C. to about 200° C.
 5. Theprocess of claim 2 wherein step (b) is conducted within a pressure rangeof about 0.001 torr to about 10 torr.
 6. The process of claim 5 whereinstep (b) is conducted within a pressure range of about 1 torr to about100 torr.
 7. The process of claim 1 wherein each of step (b) and step(c) independently is continuous.
 8. The process of claim 1 wherein step(b) is conducted with at least one solvent removal apparatus selectedfrom the group consisting of a rising film evaporator, a falling filmstripper, a thin film evaporator, a wiped film evaporator, a molecularstill, a centrifuge, a filter, and a short path evaporator.
 9. Theprocess of claim 8 wherein a rising film evaporator comprises a tubularheat exchanger.
 10. The process of claim 8 wherein each solvent removalapparatus removes between about 80% and about 90% of the solvent. 11.The process of claim 1 wherein the macrocyclic oligoester comprises amacrocyclic co-oligoester.
 12. The process of claim 1 wherein themacrocyclic oligoester substantially free from the solvent contains lessthan about 200 ppm of the solvent.
 13. The process of claim 1 whereinthe macrocyclic oligoester substantially free from the solvent containsless than about 10 ppm of the solvent.
 14. The process of claim 1wherein the solution of a macrocyclic oligoester and a solvent comprisesbetween about 1% and about 50% by weight of macrocyclic oligoester. 15.The process of claim 1 wherein the macrocyclic oligoester comprises astructural repeat unit selected from the group consisting of ethyleneterephthalate, propylene terephthalate, 1,3-propylene terephthalate,1,4-butylene terephthalate, 1,4-cyclohexylenedimethylene terephthalate,and 1,2-ethylene 2,6-naphthalenedicarboxylate.
 16. The process of claim1 wherein step (b) comprises removing the solvent at an elevatedtemperature and a reduced pressure using a first rising film evaporator;a second rising film evaporator; and a falling film stripper.
 17. Theprocess of claim 1 wherein step (b) comprises removing the solvent at anelevated temperature and a reduced pressure using a first rising filmevaporator; a first flash device; a first condenser; a second risingfilm evaporator; a second flash device; a second condenser; a liquidreceiver; a sparger, and a falling film stripper.
 18. The process ofclaim 1 wherein step (b) comprises removing the solvent at an elevatedtemperature and a reduced pressure using a first short path evaporator,a second short path evaporator; and a falling film stripper.
 19. Theprocess of claim 1 wherein step (b) comprises removing the solvent at anelevated temperature and a reduced pressure using a first short pathevaporator; a first flash device; first condenser; a second short pathevaporator; a second flash device; a second condenser; a liquidreceiver; and a falling film stripper.
 20. A process for shaping apartially-crystallized macrocyclic oligoester, the process comprisingthe steps of: (a) providing a substantially solvent-free moltenmacrocyclic oligoester, the macrocyclic oligoester comprising astructural repeat unit of formula (I):

 wherein R is an alkylene, a cycloalkylene, or a mono- orpolyoxyalkylene group and A is a divalent aromatic or alicyclic group;(b) shearing the substantially solvent-free molten macrocyclicoligoester to form a partially-crystallized macrocyclic oligoester; and(c) shaping the partially-crystallized macrocyclic oligoester.
 21. Theprocess of claim 20 wherein each of step (b) and step (c) independentlyis continuous.
 22. The process of claim 20 wherein step (b) comprisesshearing the substantially solvent free macrocyclic oligoester at atemperature below the melting point of the macrocyclic oligoester. 23.The process of claim 22 wherein step (b) is conducted in a shear mixerat a shear mixer temperature between about 100° C. and about 165° C. 24.The process of claim 23 wherein step (b) is conducted in a shear mixerat a temperature between about 145° C. and about 155° C.
 25. The processof claim 20 wherein shearing the substantially solvent free moltenmacrocyclic oligoester comprises extruding the substantially solventfree molten macrocyclic oligoester at a temperature below the meltingpoint of the macrocyclic oligoester.
 26. The process of claim 25 whereinstep (b) is conducted in an extruder at a temperature between about 100°C. and about 165° C.
 27. The process of claim 26 wherein step (b) isconducted in an extruder at a temperature between about 145° C. andabout 155° C.
 28. The process of claim 20 wherein step (c) comprisesshaping the partially-crystallized macrocyclic oligoester into a shapeselected from the group consisting of a pellet, a pastille, and a flake.29. The process of claim 20 comprising the step of collecting theproduct of step (c).
 30. The process of claim 20 comprising adding atleast one additive to the substantially solvent-free molten macrocyclicoligoester.
 31. The process of claim 30 wherein the at least oneadditive is selected from the group consisting of a colorant, a pigment,a magnetic material, an anti-oxidant, a UV stabilizer, a plasticizer, afire-retardant, lubricant, and a mold releaser.
 32. The process of claim30 wherein the at least one additive is selected from the groupconsisting of fumed silicate, titanium dioxide, calcium carbonate,chopped fibers, fly ash, glass microspheres, micro-balloons, crushedstone, nanoclay, linear polymers, and monomers.
 33. The process of claim20 comprising adding a catalyst to the substantially solvent-free moltenmacrocyclic oligoester.
 34. A process for making a prepreg of amacrocyclic oligoester and a polymerization catalyst, the processcomprising the steps of: (a) providing a mixture of a molten macrocyclicoligoester and a polymerization catalyst, wherein the mixture issubstantially free from solvent, the macrocyclic oligoester comprises astructural repeat unit of formula (1):

 wherein R is an alkylene, a cycloalkylene, or a mono- orpolyoxyalkylene group and A is a divalent aromatic or alicyclic group;and (b) depositing the mixture of the molten macrocyclic oligoester andthe polymerization catalyst onto a fabric material.
 35. The process ofclaim 34 wherein the molten macrocyclic oligoester contains less thanabout 200 ppm of solvent.
 36. The process of claim 34 comprisingpartially crystallizing the mixture of the molten macrocyclic oligoesterand the polymerization catalyst to form a partially-crystallized mixtureof the macrocyclic oligoester and the polymerization catalyst, anddepositing the partially-crystallized mixture of the macrocyclicoligoester and the polymerization catalyst onto a fabric material. 37.The process of claim 36 comprising shear-mixing the mixture of themolten macrocyclic oligoester and the polymerization catalyst.
 38. Theprocess of claim 37 wherein shear-mixing is conducted within atemperature range of about 145° C. and about 155° C.
 39. The process ofclaim 36 wherein step (a) comprises extruding the mixture of macrocyclicoligoester and polymerization catalyst.
 40. The process of claim 39wherein extruding is conducted within a temperature range of about 145°C. and about 155° C.
 41. The process of claim 36 comprising the step ofshaping the fabric material.
 42. The process of claim 36 comprising thestep of depositing the partially-crystallized mixture of the macrocyclicoligoester and the polymerization catalyst onto the fabric material in apre-selected array.
 43. The process of claim 34 wherein the moltenmacrocyclic oligoester comprises at least one additive selected from thegroup consisting of a colorant, a pigment, a magnetic material, ananti-oxidant, a UV stabilizer, a plasticizer, a fire-retardant, alubricant, and a mold release.
 44. The process of claim 34 wherein thepolymerization catalyst is an organotin catalyst or an organo-titanatecatalyst.
 45. The process of claim 34 wherein the fabric materialcomprises at least one material selected from the group of fiber tow,fiber web, fiber mat, felt, non woven material, random, and wovenmaterial.
 46. A process for making a prepreg of a macrocyclic oligoesterand a polymerization catalyst, the process comprising the steps of: (a)providing continuously a mixture of a molten macrocyclic oligoester anda polymerization catalyst, wherein the mixture is substantially freefrom solvent and the macrocyclic oligoester comprises a structuralrepeat unit of formula (I):

 wherein R is an alkylene, a cycloalkylene, or a mono- orpolyoxyalkylene group and A is a divalent aromatic or alicyclic group;(b) crystallizing partially the mixture of the macrocyclic oligoesterand the polymerization catalyst to form a partially-crystallized mixtureof the macrocyclic oligoester and the polymerization catalyst; and (c)depositing the partially-crystallized mixture of the macrocyclicoligoester and the polymerization catalyst onto a fabric material. 47.The process of claim 46 wherein each of steps (b) through (c)independently is continuous.
 48. The process of claim 46 wherein thefabric material comprises at least one material selected from the groupof fiber tow, fiber web, fiber mat, felt, non woven material, random,and woven material.
 49. A process for formulating a macrocyclicoligoester, the process comprising the steps of: (a) providing asolution comprising a macrocyclic oligoester and a solvent, themacrocyclic oligoester comprising a structural repeat unit of formula(I):

 wherein R is an alkylene, a cycloalkylene, or a mono- orpolyoxyalkylene group and A is a divalent aromatic or alicyclic group;(b) removing continuously the solvent at an elevated temperature betweenabout 180° C. and about 200° C., and a pressure between aboutatmospheric pressure and about 10 torr, to produce a substantiallysolvent-free molten macrocyclic oligoester; (c) shearing thesubstantially solvent-free molten macrocyclic oligoester at atemperature below the melting point of the molten macrocyclic oligoesterto form a partially-crystallized macrocyclic oligoester; and (d) shapingthe partially-crystallized macrocyclic oligoester into a shape selectedfrom the group consisting of a pellet, a pastille, and a flake.
 50. Theprocess of claim 49 wherein step (b) comprises using a first rising filmevaporator; a first flash device; a first condenser; a second risingfilm evaporator; a second flash device; a second condenser; a liquidreceiver; a sparger; and a falling film stripper.
 51. The process ofclaim 49 wherein step (b) comprises using a first short path evaporator;a first flash device; a first condenser; a second short path evaporator;a second flash device; a second condenser; a liquid receiver; and afalling film stripper.